Semiconductor materials prepared from rylene-(π-acceptor)copolymers

Abstract

Disclosed are new semiconductor materials prepared from rylene-(π-acceptor) copolymers. Such copolymers can exhibit high n-type carrier mobility and/or good current modulation characteristics. In addition, the polymers of the present teachings can possess certain processing advantages such as solution-processability and/or good stability at ambient conditions.

What is claimed is: 
     
       1. A polymer represented by formula: 
       
         
           
           
               
               
           
         
       
       wherein:
 M 1  is an optionally substituted aromatic imide selected from: 
 
       
         
           
           
               
               
           
         
       
       wherein:
 R 1 , at each occurrence, is independently selected from H, a C 1-40  alkyl group, a C 2-40  alkenyl group, a C 1-40  haloalkyl group, and 1-4 cyclic moieties, 
 wherein: 
 each of the C 1-40  alkyl group, the C 2-40  alkenyl group, and the C 1-40  haloalkyl group can be optionally substituted with 1-10 substituents independently selected from a halogen, —CN, NO 2 , OH, —NH 2 , —NH(C 1-20  alkyl), —N(C 1-20  alkyl) 2 , —S(O) 2 OH, —CHO, —C(O)—C 1-20  alkyl, —C(O)OH, —C(O)—OC 1-20  alkyl, —C(O)NH 2 , —C(O)NH—C 1-20  alkyl, —C(O)N(C 1-20  alkyl) 2 , —OC 1-20  alkyl, —SiH 3 , —SiH(C 1-20  alkyl) 2 , —SiH 2 (C 1-20  alkyl), and —Si(C 1-20  alkyl) 3 ; 
 each of the C 1-40  alkyl group, the C 2-40  alkenyl group, and the C 1-40  haloalkyl group can be covalently bonded to the imide nitrogen atom via an optional linker, and 
 each of the 1-4 cyclic moieties can be the same or different, can be covalently bonded to each other or the imide nitrogen via an optional linker, and can be optionally substituted with 1-5 substituents independently selected from a halogen, oxo, —CN, NO 2 , OH, ═C(CN) 2 , —NH 2 , —NH(C 1-20  alkyl), —N(C 1-20  alkyl) 2 , —S(O) 2 OH, —CHO, —C(O)OH, —C(O)—C 1-20  alkyl, —C(O)—OC 1-20  alkyl, —C(O)NH 2 , —C(O)NH—C 1-20  alkyl, —C(O)N(C 1-20  alkyl) 2 , —SiH 3 , —SiH(C 1-20  alkyl) 2 , 
 —SiH 2 C 1-20  alkyl), —Si(C 1-20  alkyl) 3 , —O—C 1-20  alkyl, —O—C 1-20  alkenyl, —O—C 1-20  haloalkyl, a C 1-20  alkyl group, a C 1-20  alkenyl group, and a C 1-20  haloalkyl group; and 
 π-1 and π-1′ are an optionally substituted fused ring moiety selected from: 
 
       
         
           
           
               
               
           
         
         wherein a° is 0 or 1; 
         M 2  is a repeating unit comprising one or more optionally substituted polycyclic moieties and has a formula selected from: 
       
       
         
           
           
               
               
           
         
         wherein: 
         π-2, at each occurrence, is independently an optionally substituted polycyclic moiety; and 
         Z, at each occurrence, is independently a linear conjugated linker; and 
       
       n is an integer between 2 and 5,000,
 wherein π-2 has a reduction potential greater than or equal to −2.2 V; 
 provided that the polymer does not have a repeating unit of the formula: 
 
       
         
           
           
               
               
           
         
       
     
     
       2. The polymer of  claim 1 , wherein M 1  is an optionally substituted aromatic imide selected from: 
       
         
           
           
               
               
           
         
         and R 1  is as defined in  claim 1 . 
       
     
     
       3. The polymer of  claim 1 , wherein each of π-1, π-1′, and π-2 independently is optionally substituted with 1-6 R a  groups; wherein:
 R a , at each occurrence, is a) halogen, b) —CN, c)  − NO 2 , d) oxo, e) —OH, f) ═C(R b ) 2 , g) a C 1-40  alkyl group, h) a C 2-40  alkenyl group, i) a C 2-40  alkynyl group, j) a C 1-40  alkoxy group, k) a C 1-40  alkylthio group, l) a C 1-40  haloalkyl group, m) a —Y—C 3-10  cycloalkyl group, n) a —Y—C 6-14  aryl group, o) a —Y—C 6-14  haloaryl group, p) a —Y-3-12 membered cycloheteroalkyl group, or q) a —Y-5-14 membered heteroaryl group, wherein each of the C 1-40  alkyl group, the C 2-40  alkenyl group, the C 2-40  alkynyl group, the C 3-10  cycloalkyl group, the C 6-14  aryl group, the C 6-14  haloaryl group, the 3-12 membered cycloheteroalkyl group, and the 5-14 membered heteroaryl group is optionally substituted with 1-4 R b  groups; 
 R b , at each occurrence, is a) halogen, b) —CN, c) —NO 2 , d) oxo, e) —OH, f) —NH 2 , g) —NH(C 1-20  alkyl), h) —N(C 1-20  alkyl) 2 , i) —N(C 1-20  alkyl)-C 6-14  aryl, j) —N(C 6-14  aryl) 2 , k) —S(O) m H, l) —S(O) m —C 1-20  alkyl, m) —S(O) 2 OH, n) —S(O) m —OC 1-20  alkyl, o) —S(O) m —OC 6-14  aryl, p) —CHO, q) —C(O)—C 1-20  alkyl, r) —C(O)—C 6-14  aryl, s) —C(O)OH, t) —C(O)—OC 1-20  alkyl, u) —C(O)—OC 6-14  aryl, v) —C(O)NH 2 , w) —C(O)NH—C 1-20  alkyl, x) —C(O)N(C 1-20  alkyl) 2 , y) —C(O)NH—C 6-14  aryl, z) —C(O)N(C 1-20  alkyl)-C 6-14  aryl, aa) —C(O)N(C 6-14  aryl) 2 , ab) —C(S)NH 2 , ac) —C(S)NH—C 1-20  alkyl, ad) —C(S)N(C 1-20  alkyl) 2 , ae) —C(S)N(C 6-14  aryl) 2 , af) —C(S)N(C 1-20  alkyl)-C 6-14  aryl, ag) —C(S)NH—C 6-14  aryl, ah) —S(O) m NH 2 , ai) —S(O) m NH(C 1-20  alkyl), aj) —S(O) m N(C 1-20  alkyl) 2 , ak) —S(O) m NH(C 6-14  aryl), al) —S(O) m (C 1-20  alkyl)-C 6-14  aryl, am) —S(O) m N(C 6-14  aryl) 2 , an) —SiH 3 , ao) —SiH(C 1-20  alkyl) 2 , ap) —SiH 2 (C 1-20  alkyl), aq) —Si(C 1-20  alkyl) 3 , ar) a C 1-20  alkyl group, as) a C 2-20  alkenyl group, at) a C 2-20  alkynyl group, au) a C 1-20  alkoxy group, av) a C 1-20  alkylthio group, aw) a C 1-20  haloalkyl group, ax) a C 3-10  cycloalkyl group, ay) a C 6-14  aryl group, az) a C 6-14  haloaryl group, ba) a 3-12 membered cycloheteroalkyl group, or bb) a 5-14 membered heteroaryl group; 
 Y, at each occurrence, is a divalent C 1-20  alkyl group, a divalent C 1-20  haloalkyl group, or a covalent bond; and 
 m, at each occurrence, is 0, 1, or 2. 
 
     
     
       4. The polymer of  claim 1 , wherein R 1 , at each occurrence, is independently selected from H, a C 1-40  alkyl group, a C 2-40  alkenyl group, a C 1-40  haloalkyl group, -L-Ar 1 , -L-Ar 1 —Ar 1 , -L-Ar 1 —R 2 , -L-Ar 1 —Ar 1 —R 2 , -L-Cy 1 , -L-Cy 1 -Cy 1 , -L-Cy 1 -R 2 , and -L-Cy 1 -Cy 1 -R 2 ;
 wherein: 
 L, at each occurrence, is independently selected from —Y—O—Y—, —Y—[S(O) m ]—Y—, —Y—C(O)—Y—, —Y—[NR c C(O)]—Y—, —Y—[C(O)NR c ]—, —Y—[SiR c   2 ]-Y—, a divalent C 1-20  alkyl group, a divalent C 1-20  alkenyl group, a divalent C 1-20  haloalkyl group, and a covalent bond; 
 wherein: 
 R c , at each occurrence, is independently H, a C 1-6  alkyl group, or a —Y—C 6-14  aryl group; 
 Ar 1 , at each occurrence, is independently a monovalent or divalent C 6-14  aryl group or a 5-14 membered heteroaryl group, each optionally substituted with 1-5 substituents independently selected from a halogen, —CN, oxo, ═C(CN) 2 , a C 1-6  alkyl group, a C 1-6  alkoxy group, and a C 1-6  haloalkyl group; and 
 Cy 1 , at each occurrence, is independently a monovalent or divalent C 3-14  cycloalkyl group or a 3-14 membered cycloheteroalkyl group, each optionally substituted with 1-5 substituents independently selected from a halogen, —CN, oxo, ═C(CN) 2 , a C 1-6  alkyl group, a C 1-6  alkoxy group, and a C 1-6  haloalkyl group; 
 R 2 , at each occurrence, is independently selected from a C 1-40  alkyl group, a C 2-40  alkenyl group, a C 1-40  haloalkyl group, a C 1-40  alkoxy group, -L′-Ar 2 , -L′-Ar 2 —Ar 2 , -L′-Ar′—R 3 , -L′-Ar 2 —Ar 2 —R 3 , -L′-Cy 2 , -L′-Cy 2 -Cy 2 , -L′-Cy 2 -R 3 , -L′-Cy 2 -Cy 2 -R 3 ; 
 wherein: 
 L′, at each occurrence, is independently selected from —Y—O—Y—, —Y—[S(O) m ]-Y—, —Y—C(O)—Y—, —Y—[NR c C(O)]—Y—, —Y—[C(O)NR c ]—, —Y—NR c —, —Y—[SiR c   2 ]-Y—, a divalent C 1-20  alkyl group, a divalent C 1-20  alkenyl group, a divalent C 1-20  haloalkyl group, and a covalent bond; 
 Ar 2 , at each occurrence, is independently a monovalent or divalent C 6-14  aryl group or a 5-14 membered heteroaryl group, each optionally substituted with 1-5 substituents independently selected from halogen, oxo, —CN, ═C(CN) 2 , a C 1-6  alkyl group, a C 1-6  alkoxy group, and a C 1-6  haloalkyl group; 
 Cy 2 , at each occurrence, is independently a monovalent or divalent C 3-14  cycloalkyl group or a 3-14 membered cycloheteroalkyl group, each optionally substituted with 1-5 substituents independently selected from a halogen, oxo, —CN, ═C(CN) 2 , a C 1-6  alkyl group, a C 1-6  alkoxy group, and a C 1-6  haloalkyl group; 
 R 3 , at each occurrence, is a C 1-40  alkyl group, a C 2-40  alkenyl group, a C 1-40  haloalkyl group, or a C 1-40  alkoxy group; 
 Y, at each occurrence, is a divalent C 1-20  alkyl group, a divalent C 1-20  haloalkyl group, or a covalent bond; and 
 m, at each occurrence, is 0, 1, or 2. 
 
     
     
       5. The polymer of  claim 1 , represented by formula: 
       
         
           
           
               
               
           
         
         wherein n is an integer between 5 and 1,000; x is a real number and 0<x≦1; and π-2 and R 1  are as defined in  claim 1 . 
       
     
     
       6. The polymer of  claim 1 , wherein R 1  is a linear or branched C 3-40  alkyl group selected from an n-hexyl group, a 1-methylpropyl group, a 1-methylbutyl group, a 1-methylpentyl group, a 1-methylhexyl group, a 1-ethylpropyl group, a 1-ethylbutyl group, a 1-3,dimethylbutyl group, and a 2-octyldodecyl group. 
     
     
       7. The polymer of  claim 1 , wherein R 1  is selected from: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
       8. The polymer of  claim 3 , wherein π-2 is selected from: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein: 
         k, k′, l and l′ independently are selected from —CR d ═, ═CR d —, —C(O)—, —C(C(CN) 2 )—; 
         p, p′, q and q′ independently are selected from —CR d ═, ═CR d —, —C(O)—, —C(C(CN) 2 )—, —O—, —S—, —N═, ═N—, —N(R d )—, —SiR d ═, ═SiR d —, and —SiR d R d —; 
         r and s independently are —CR d R d — or —C(C(CN) 2 )—; 
         u, u′, v and v′ independently are selected from —CR d ═, ═CR d —, —C(O)—, —C(C(CN) 2 )—, —S—, —S(O)—, —S(O) 2 —, —O—, —N═, ═N—, —SiR d =, —SiR d R d —, —CR d R d —CR d R d —, and —CR d ═CR d —; 
         R d , at each occurrence, independently is H or R a ; and 
         R a  is as defined in  claim 3 . 
       
     
     
       9. The polymer of  claim 3 , wherein π-2 is selected from: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein R d , at each occurrence, independently is H or R a ; and R a  is as defined in  claim 3 . 
       
     
     
       10. The polymer of  claim 1 , wherein π-2 is a polycyclic moiety comprising a Spiro atom or substituted with 1-4 groups selected from an oxo group and a dicyanovinylidenyl group. 
     
     
       11. The polymer of  claim 1 , wherein the polymer is 
       
         
           
           
               
               
           
         
         or wherein R 1  and n are as defined in  claim 1 . 
       
     
     
       12. The polymer of  claim 1 , wherein the polymer is 
       
         
           
           
               
               
           
         
         wherein R 1  and n are as defined in  claim 1 . 
       
     
     
       13. The polymer of  claim 1 , wherein the polymer is selected from: 
       
         
           
           
               
               
           
         
         wherein R 1  and n are as defined in  claim 1 . 
       
     
     
       14. The polymer of  claim 1 , wherein the polymer is selected from: 
       
         
           
           
               
               
           
         
         wherein R 1  and n are as defined in  claim 1 . 
       
     
     
       15. A polymer represented by formula I or formula I′: 
       
         
           
           
               
               
           
         
       
       wherein: 
       π-1 and π-1′ independently are a cyclic moiety optionally substituted with 1-4 R a  groups; 
       π-2 is a 7-conjugated moiety having a reduction potential greater than about −2.6 V and optionally substituted with 1-6 R a  groups;
 wherein: 
 R a , at each occurrence, is a) halogen, b) —CN, c) —NO 2 , d) oxo, e) —OH, f) ═C(R b ) 2 , g) a C 1-40  alkyl group, h) a C 2-40  alkenyl group, i) a C 2-40  alkynyl group, j) a C 1-40  alkoxy group, k) a C 1-40  alkylthio group, l) a C 1-40  haloalkyl group, m) a —Y—C 3-10  cycloalkyl group, n) a —Y—C 6-14  aryl group, o) a —Y—C 6-14  haloaryl group, p) a —Y-3-12 membered cycloheteroalkyl group, or q) a —Y-5-14 membered heteroaryl group, wherein each of the C 1-40  alkyl group, the C 2-40  alkenyl group, the C 2-40  alkynyl group, the C 3-10  cycloalkyl group, the C 6-14  aryl group, the C 6-14  haloaryl group, the 3-12 membered cycloheteroalkyl group, and the 5-14 membered heteroaryl group is optionally substituted with 1-4 R b  groups; 
 R b , at each occurrence, is a) halogen, b) —CN, c) —NO 2 , d) oxo, e) f) —NH 2 , g) —NH(C 1-20  alkyl), h) —N(C 1-20  alkyl) 2 , i) —N(C 1-20  alkyl)-C 6-14  aryl, j) —N(C 6-14  aryl) 2 , k) —S(O) m H, l) —S(O) m —C 1-20  alkyl, m) —S(O) 2 OH, n) —S(O) m —OC 1-20  alkyl, o) —S(O) m —OC 6-14  aryl, p) —CHO, q) —C(O)—C 1-20  alkyl, r) —C(O)—C 6-14  aryl, s) —C(O)OH, t) —C(O)—OC 1-20  alkyl, u) —C(O)—OC 6-14  aryl, v) —C(O)NH 2 , w) —C(O)NH—C 1-20  alkyl, x) —C(O)N(C 1-20  alkyl) 2 , y) —C(O)NH—C 6-14  aryl, z) —C(O)N(C 1-20  alkyl)-C 6-14  aryl, aa) —C(O)N(C 6-14  aryl) 2 , ab) —C(S)NH 2 , ac) —C(S)NH—C 1-20  alkyl, ad) —C(S)N(C 1-20  alkyl 2 , ae) —C(S)N(C 6-14  aryl) 2 , af) —C(S)N(C 1-20  alkyl)-C 6-14  aryl, ag) —C(S)NH—C 6-14  aryl, ah) —S(O) m NH 2 , ai) —S(O) m NH(C 1-20  alkyl), aj) —S(O) m N(C 1-20  alkyl) 2 , ak) —S(O) m NH(C 6-14  aryl), al) —S(O) m N(C 1-20  alkyl)-C 6-14  aryl, am) —S(O) m N(C 6-14  aryl) 2 , an) —SiH 3 , ao) —SiH(C 1-20  alkyl) 2 , ap) —SiH 2 (C 1-20  alkyl), aq) Si(C 1-20  alkyl) 3 , ar) a C 1-20  alkyl group, as) a C 2-20  alkenyl group, at) a C 2-20  alkynyl group, au) a C 1-20  alkoxy group, av) a C 1-20  alkylthio group, aw) a C 1-20  haloalkyl group, ax) a C 3-10  cycloalkyl group, ay) a C 6-14  aryl group, az) a C 6-14  haloaryl group, ba) a 3-12 membered cycloheteroalkyl group, or bb) a 5-14 membered heteroaryl group; 
 Y, at each occurrence, is a divalent C 1-20  alkyl group, a divalent C 1-20  haloalkyl group, or a covalent bond; and 
 m, at each occurrence, is 0, 1, or 2; 
 R 1 , at each occurrence, is independently selected from H, a C 1-40  alkyl group, a C 2-40  alkenyl group, a C 1-40  haloalkyl group, -L-Ar 1 , -L-Ar 1 —Ar 1 , -L-Ar 1 —R 2 , -L-Ar 1 —Ar 1 —R 2 , -L-Cy 1 , -L-Cy 1 -Cy 1 , -L-Cy 1 -R 2 , and -L-Cy 1 -Cy 1 -R 2 ; 
 wherein: 
 L, at each occurrence, is independently selected from —Y—O—Y—, —Y—[S(O) m ]—Y—, —Y—C(O)—Y—, —Y—[NR c C(O)]—Y—, —Y—[C(O)NR c ]—, —Y—NR c —, —Y—[SiR c   2 ]—Y—, a divalent C 1-20  alkyl group, a divalent C 1-20  alkenyl group, a divalent C 1-20  haloalkyl group, and a covalent bond;
 wherein: 
 R c , at each occurrence, is independently H, a C 1-6  alkyl group, or a —Y—C 6-14  aryl group; 
 
 Ar 1 , at each occurrence, is independently a monovalent or divalent C 6-14  aryl group or a 5-14 membered heteroaryl group, each optionally substituted with 1-5 substituents independently selected from a halogen, —CN, oxo, ═C(CN) 2 , a C 1-6  alkyl group, a C 1-6  alkoxy group, and a C 1-6  haloalkyl group; and 
 Cy 1 , at each occurrence, is independently a monovalent or divalent C 3-14  cycloalkyl group or a 3-14 membered cycloheteroalkyl group, each optionally substituted with 1-5 substituents independently selected from a halogen, —CN, oxo, ═C(CN) 2 , a C 1-6  alkyl group, a C 1-6  alkoxy group, and a C 1-6  haloalkyl group; 
 R 2 , at each occurrence, is independently selected from a C 1-40  alkyl group, a C 2-40  alkenyl group, a C 1-40  haloalkyl group, a C 1-40  alkoxy group, -L′-Ar 2 , -L′-Ar c —Ar 2 , -L′-Ar 2 —R 3 , -L′-Ar 2 —Ar 2 —R 3 , -L′-Cy 2 , -L′-Cy 2 -Cy 2 , -L′-Cy 2 -R 3 , -L′-Cy 2 -Cy 2 -R 3 ; 
 wherein: 
 L′, at each occurrence, is independently selected from —Y—O—Y—, —Y—[S(O) m ]—Y—, —Y—[C(O)—Y—, —Y—[NR c C(O)]—Y—, —Y—[C(O)NR c ]—, —Y—NR c —, —Y—[SiR c   2 ]—Y—, a divalent C 1-20  alkyl group, a divalent C 1-20  alkenyl group, a divalent C 1-20  haloalkyl group, and a covalent bond; 
 Ar c , at each occurrence, is independently a monovalent or divalent C 6-14  aryl group or a 5-14 membered heteroaryl group, each optionally substituted with 1-5 substituents independently selected from halogen, oxo, —CN, ═C(CN) 2 , a C 1-6  alkyl group, a C 1-6  alkoxy group, and a C 1-6  haloalkyl group; 
 Cy 2 , at each occurrence, is independently a monovalent or divalent C 3-14  cycloalkyl group or a 3-14 membered cycloheteroalkyl group, each optionally substituted with 1-5 substituents independently selected from a halogen, oxo, —CN, ═C(CN) 2 , a C 1-6  alkyl group, a C 1-6  alkoxy group, and a C 1-6  haloalkyl group; 
 R 3 , at each occurrence, is a C 1-40  alkyl group, a C 2-40  alkenyl group, a C 1-40  haloalkyl group, or a C 1-40  alkoxy group; and 
 n is an integer in the range from 2 to 5,000. 
 
     
     
       16. The polymer of  claim 15 , wherein 7-2 has a reduction potential greater than or equal to about −1.2 V. 
     
     
       17. The polymer of  claim 15 , wherein π-2 is a polycyclic moiety optionally substituted with 1-6 R a  groups. 
     
     
       18. A composition comprising the polymer of  claim 1  dissolved or dispersed in a liquid medium. 
     
     
       19. The composition of  claim 18 , wherein the liquid medium comprises water or an organic solvent. 
     
     
       20. The composition of  claim 18 , the composition further comprising at least one additive. 
     
     
       21. The composition of  claim 20 , wherein the additive is independently selected from the group consisting of a detergent, a dispersant, a binding agent, a compatiblizing agent, a curing agent, an initiator, a humectant, an antifoaming agent, a wetting agent, a pH modifier, a biocide, and a bactereriostat. 
     
     
       22. An article of manufacture comprising the polymer of  claim 1 . 
     
     
       23. The article of manufacture of  claim 22 , wherein the article of manufacture is an electronic device, an optical device, or an optoelectronic device. 
     
     
       24. A thin film semiconductor comprising the polymer of  claim 1 . 
     
     
       25. A composite comprising a substrate and the thin film semiconductor of  claim 24  deposited on the substrate. 
     
     
       26. A field effect transistor device comprising the thin film semiconductor of  claim 24 . 
     
     
       27. A field effect transistor device comprising the composite of  claim 25 . 
     
     
       28. The field effect transistor device of  claim 26 , wherein the field effect transistor has a structure selected from top-gate bottom-contact structure, bottom-gate top-contact structure, top-gate top-contact structure, and bottom-gate bottom-contact structure. 
     
     
       29. The field effect transistor device of  claim 26  comprising a dielectric material, wherein the dielectric material comprises an organic dielectric material, an inorganic dielectric material, or a hybrid organic/inorganic dielectric material. 
     
     
       30. A photovoltaic device comprising the thin film semiconductor of  claim 24 . 
     
     
       31. A photovoltaic device comprising the composite of  claim 25 . 
     
     
       32. The photovoltaic device of  claim 30  comprising a p-type semiconducting material adjacent to the polymer. 
     
     
       33. An organic light emitting device comprising the thin film semiconductor of  claim 24 . 
     
     
       34. An organic light emitting device comprising the composite of  claim 25 . 
     
     
       35. A method of making an article of manufacture comprising depositing a composition of  claim 26  onto a substrate. 
     
     
       36. The method of  claim 35 , wherein depositing the composition comprises at least one of printing, spin coating, drop-casting, zone casting, dip coating, blade coating, and spraying. 
     
     
       37. The method of  claim 36 , wherein printing is selected from gravure printing, inkjet printing, flexographic printing, screen printing, pad printing, offset printing, and lithographic printing.